WO2009116608A1 - Composition de résine renforcée par des fibres longues et article moulé à base de cette composition - Google Patents

Composition de résine renforcée par des fibres longues et article moulé à base de cette composition Download PDF

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WO2009116608A1
WO2009116608A1 PCT/JP2009/055388 JP2009055388W WO2009116608A1 WO 2009116608 A1 WO2009116608 A1 WO 2009116608A1 JP 2009055388 W JP2009055388 W JP 2009055388W WO 2009116608 A1 WO2009116608 A1 WO 2009116608A1
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resin
fiber reinforced
component
long fiber
thermoplastic resin
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PCT/JP2009/055388
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English (en)
Japanese (ja)
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合田　宏史
岩下　亨
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株式会社プライムポリマー
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Application filed by 株式会社プライムポリマー filed Critical 株式会社プライムポリマー
Priority to JP2010503917A priority Critical patent/JPWO2009116608A1/ja
Priority to CN200980109941.6A priority patent/CN102159627B/zh
Priority to US12/922,348 priority patent/US9359492B2/en
Priority to EP09722098.2A priority patent/EP2256150B1/fr
Priority to BRPI0908954A priority patent/BRPI0908954A2/pt
Publication of WO2009116608A1 publication Critical patent/WO2009116608A1/fr
Priority to US15/139,547 priority patent/US20160237269A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/12—Applications used for fibers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils

Definitions

  • the present invention relates to a long fiber reinforced resin composition and a molded body thereof.
  • module parts made of the long fiber reinforced resin compositions are used as automotive module parts that require high strength.
  • the reinforcing fiber sometimes appears as a lump on the module component surface.
  • module parts made of the long fiber reinforced resin composition have to be used as parts in places where the required level of appearance is low, or the surface thereof needs to be coated.
  • Patent Document 1 fiber reinforced resin compositions having improved appearance of the obtained molded articles have been reported (Patent Document 1 and Patent Document 2).
  • Patent Document 2 a molded product obtained from the above-described fiber reinforced resin composition does not completely satisfy the high appearance required by, for example, automobile module parts, and further improvement in appearance has been demanded.
  • An object of the present invention is to provide a long fiber reinforced resin composition that provides a molded article having good opening properties of reinforcing fibers at the time of molding and having excellent appearance.
  • the present inventors have used a resin having a short relaxation time for both the long fiber reinforced thermoplastic resin pellet and the dilution resin, and when using a composition comprising these pellets and the dilution resin, The present inventors have found that the fiber mass on the surface of the molded body can be prevented from being raised, and the present invention has been completed. According to the present invention, the following long fiber reinforced resin composition and the like are provided. 1.
  • a long fiber reinforced resin composition comprising the following component (A) and component (B), The content of the component (A) is 50 to 90 wt% and the content of the component (B) is 10 to 50 wt%; A long fiber reinforced resin composition in which the content of reinforcing fibers contained in the component (A) is 20 to 60 wt% with respect to the total amount of the long fiber reinforced resin composition.
  • Component (A) Long fiber reinforced thermoplastic resin pellets comprising a thermoplastic resin, a modified polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof, and reinforcing fibers and satisfying the following (A-1) to (A-4).
  • the long fiber reinforced resin composition of the present invention is a long fiber comprising a modified polyolefin resin modified with a thermoplastic resin, an unsaturated carboxylic acid or a derivative thereof (hereinafter sometimes simply referred to as a modified polyolefin resin) and a reinforcing fiber.
  • a fiber reinforced thermoplastic resin pellet (component (A)) is included.
  • the long fiber reinforced thermoplastic resin pellet as the component (A) satisfies the following (A-1) to (A-4).
  • A-1 The thermoplastic resin has a melt index (resin temperature: 230 ° C., load: 21.18 N) of 100 to 250 g / 10 min.
  • A-3) The content of the reinforcing fiber is 40. ⁇ 70wt%
  • A-4) The content of the modified polyolefin resin is 1 to 5 wt%
  • the thermoplastic resin contained in the long fiber reinforced thermoplastic resin pellet (component (A)) is not particularly limited as long as the above (A-1) and (A-2) are satisfied.
  • a polyolefin resin, a polystyrene resin, A polycarbonate resin or the like can be used.
  • the polyolefin resin includes a polyethylene resin such as an ethylene homopolymer, a polypropylene resin such as a propylene homopolymer, and an ethylene-propylene copolymer resin such as an ethylene-propylene block copolymer.
  • the polystyrene resin include atactic polystyrene and syndiotactic polystyrene.
  • the said thermoplastic resin may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the melt index of the thermoplastic resin (resin temperature: 230 ° C., load: 21.18 N) is 100 to 250 g / 10 minutes, preferably 100 to 150 g / 10 minutes.
  • the melt index of the thermoplastic resin is less than 100 g / 10 minutes, the reinforcing fibers may not be easily opened during molding.
  • the melt index of the thermoplastic resin is more than 250 g / 10 minutes, the strength of the long fiber reinforced thermoplastic resin pellet may be lowered.
  • thermoplastic resin In order to adjust the melt index of the thermoplastic resin within the above range, for example, in the production of a thermoplastic resin, the molecular weight is adjusted by adjusting the hydrogen concentration during polymerization, etc., decomposed with a peroxide, or melted. A resin having a different index may be blended or kneaded.
  • a method for producing a thermoplastic resin for example, a known method such as a method for producing a polypropylene resin composition described in JP-A-11-071431, JP-A-2002-234976, and JP-A-2002-249624 is known. Manufacturing methods can be used.
  • G ′′ ⁇ ⁇ that is, G ′ ⁇ G ′′ is 0.1 (sec) or less.
  • (Relaxation time ⁇ ⁇ 0.1 (sec)) When the relaxation time ⁇ exceeds 0.1 (sec), the appearance of the molded product may be defective.
  • the relaxation time ⁇ is usually 0.01 to 0.1 (sec), preferably 0.02 to 0.05 (sec).
  • the relaxation time ⁇ When an external force is applied to a material system in an equilibrium state, and after reaching a new equilibrium state or steady state, when the external force is removed, the phenomenon that the system recovers to the initial equilibrium state by the internal motion of the system is called a relaxation phenomenon.
  • a characteristic time constant that is a measure of the time required for relaxation is called relaxation time.
  • the molten polymer is flowed. At this time, the molecular chains are stretched and aligned in the flow direction (this is referred to as “orientation”).
  • orientation the stress applied to the molecules disappears, and each molecular chain begins to move and eventually turns in a selfish direction (this is called “relaxation of molecular chains”).
  • the relaxation time ⁇ becomes short (small)
  • G ′′ is large, and there are many components showing viscous properties in the thermoplastic resin, that is, the molecular weight of the resin is small and the molecular weight is small. Means a narrow distribution.
  • the molecular weight distribution is changed by decomposing with a peroxide or the like (particularly, a resin having a small ⁇ can be obtained by decomposing at a high magnification from a high molecular weight one).
  • (2) Mixing multiple resins with different molecular weight distributions (It is effective to make a resin with a narrow molecular weight distribution by combining a highly active catalyst or using a large amount of peroxide to increase the decomposition rate. ).
  • Adjust each polymerization condition of multistage polymerization (however, it may be industrially disadvantageous in terms of cost). (4) Selection of polymerization catalyst
  • the modified polyolefin resin modified with the unsaturated carboxylic acid or derivative thereof contained in the long fiber reinforced thermoplastic resin pellet has a functional group such as a carboxyl group or a carboxylic anhydride group in the polyolefin resin.
  • a functional group such as a carboxyl group or a carboxylic anhydride group in the polyolefin resin.
  • the polyolefin resin to be modified include the above-described polyethylene resin and polypropylene resin.
  • a polypropylene resin or a mixture thereof is used as the thermoplastic resin contained in the long fiber reinforced thermoplastic resin pellet, it is preferable to use a modified polypropylene resin as the modified polyolefin resin.
  • the modified polypropylene resin includes a modified propylene homopolymer, a modified propylene- ⁇ -olefin random copolymer, a modified propylene- ⁇ -olefin block copolymer, and the like.
  • Graft modification or copolymerization can be used as a modification method of the polyolefin resin.
  • unsaturated carboxylic acid used for modification include acrylic acid, methacrylic acid, maleic acid, nadic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, sorbic acid, mesaconic acid, angelic acid, and phthalic acid. It is done.
  • the derivatives include acid anhydrides, esters, amides, imides, metal salts, and the like, such as maleic anhydride, itaconic anhydride, citraconic anhydride, nadic anhydride, phthalic anhydride, methyl acrylate, Examples include methyl acid, ethyl acrylate, butyl acrylate, maleic acid monoethyl ester, acrylamide, maleic acid monoamide, maleimide, N-butylmaleimide, sodium acrylate, and sodium methacrylate.
  • unsaturated dicarboxylic acids and derivatives thereof are preferable, and maleic anhydride or phthalic anhydride is particularly preferable.
  • the carboxylic acid addition amount of the modified polyolefin resin is preferably 0.1 to 14% by weight, more preferably 0.8 to 8% by weight. Acid addition amount is determined by measuring the IR spectrum of the resin, determined from the area of the peak of 1,670cm -1 ⁇ 1,810cm -1.
  • the modification of the polyolefin-based resin may be performed in advance prior to the production of the long fiber reinforced thermoplastic resin pellets, or may be performed in the melt-kneading process in the production of the pellets.
  • an appropriate amount of an acid-modified polyolefin resin is added to the thermoplastic resin when producing the long fiber reinforced thermoplastic resin pellets.
  • the polyolefin resin and the unsaturated carboxylic acid or derivative thereof are kneaded in an extruder using an organic peroxide, and the unsaturated carboxylic acid or derivative thereof is graft copolymerized and modified.
  • organic peroxide include benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile, dicumyl peroxide, t-butyl hydroperoxide, ⁇ , ⁇ ′-bis (t-butylperoxydiisopropyl).
  • Benzene bis (t-butyldioxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylper) And (oxy) hexyne-3, di-t-butyl peroxide, cumene hydroperoxide, and the like.
  • the content of the modified polyolefin resin is 1 to 5 wt%, preferably 1.5 to 3.5 wt% of the entire long fiber reinforced thermoplastic resin pellet (component (A)).
  • component (A) the content of the modified polyolefin resin is less than 1 wt%, the interfacial adhesion between the fiber and the resin is lowered, and the strength may be lowered.
  • the content of the modified polyolefin resin is more than 5 wt%, the overall molecular weight is lowered, and the strength may be lowered.
  • the melt index (resin temperature: 230 ° C., load: 21.18 N) of the modified polyolefin resin is usually 150 to 350 g / 10 min.
  • the reinforcing fiber contained in the long fiber reinforced thermoplastic resin pellet (component (A)) is not particularly limited, and examples thereof include organic fibers such as carbon and nylon, inorganic fibers such as basalt and glass fibers, preferably glass fibers. It is. Glass fibers such as E glass (Electrical glass), C glass (Chemical glass), A glass (Alkali glass), S glass (High strength glass), and alkali-resistant glass are melt-spun into filamentous fibers. Can be mentioned.
  • a continuous glass fiber bundle is used as a raw material for the long glass fiber, which is commercially available as glass roving.
  • the average fiber diameter is 3 to 30 ⁇ m
  • the number of filaments is 400 to 10,000
  • the tex count is 300 to 20,000 g / km.
  • the average fiber diameter is 13 to 20 ⁇ m
  • the number of bundles is 1,000 to 6,000. More preferably, the average fiber diameter is 16 to 18 ⁇ m, and the number of converged fibers is 3,000 to 5,000.
  • a plurality of fiber bundles can be bundled and used as disclosed in JP-A-6-1114830.
  • the fiber length of the glass fiber in the pellet is usually 4 to 8 mm, preferably 5 to 7 mm, and the fiber diameter is preferably 10 to 20 ⁇ m, more preferably 13 to 18 ⁇ m.
  • the content of the reinforcing fiber is 40 to 70 wt%, preferably 45 to 60 wt% of the entire long fiber reinforced thermoplastic resin pellet (component (A)). If the reinforcing fiber content is less than 40 wt%, the productivity may decrease. On the other hand, when the content of the reinforcing fiber is more than 70 wt%, the amount of the glass fiber is increased and there is a possibility that the unopened glass fiber is increased.
  • the surface of the reinforcing fiber can be provided with functional groups by various surface treatment methods such as electrolytic treatment and sizing agent treatment.
  • a sizing agent is preferably used, and a sizing agent including a coupling agent is particularly preferably used.
  • adhesion with a thermoplastic resin is imparted, and a molded article having good strength and appearance can be obtained.
  • the sizing agent examples include those containing a coupling agent as described in JP-A No. 2003-253563, for example.
  • the coupling agent can be appropriately selected from so-called silane coupling agents such as aminosilane and epoxy silane, and coupling agents conventionally known as titanium coupling agents.
  • the sizing agent preferably includes a resin emulsion for easy handling.
  • a resin emulsion contained in the sizing agent urethane-based, olefin-based, acrylic-based, nylon-based, butadiene-based, epoxy-based and the like can be used, and among these, urethane-based or olefin-based is preferably used.
  • the urethane-based sizing agent is usually an oil-modified type, a moisture-curing type, and a polyisocyanate obtained by polyaddition reaction of a diisocyanate compound and a polyhydric alcohol in a proportion of 50% by weight or more.
  • Either a one-component type such as a block type, or a two-component type such as a catalyst curable type or a polyol curable type can be used.
  • the Bondic series and Hydran series are representative.
  • an aqueous urethane for example, a modified polyolefin-based resin modified with an unsaturated carboxylic acid or a derivative thereof can be used.
  • the long fiber reinforced thermoplastic resin pellet (component (A)) comprising the thermoplastic resin, the modified polyolefin resin and the reinforcing fiber described above can be produced by a known method such as a drawing method. A part of the components may be separately melt-kneaded and then mixed (blended).
  • the long fiber reinforced thermoplastic resin pellet has a larger aspect ratio of the fibers in the composition, and it is easy to obtain a composition having high strength.
  • the shape of the long fiber reinforced thermoplastic resin pellet is usually columnar.
  • the pellet length of the long fiber reinforced thermoplastic resin pellet is preferably 4 mm to 8 mm, more preferably 5 mm to 7 mm.
  • the pellet length of the long fiber reinforced thermoplastic resin pellet is less than 4 mm, the effect of improving rigidity, heat resistance and impact strength is low, and warping deformation may be increased.
  • the pellet length of the long fiber reinforced thermoplastic resin pellets exceeds 8 mm, molding may be difficult.
  • it is preferable that the reinforcing fibers having the same fiber length of 4 mm to 8 mm are arranged substantially parallel to each other in the long fiber reinforced thermoplastic resin pellet.
  • Long fiber reinforced thermoplastic resin pellets can be easily cut by guiding the roving of thousands of reinforcing fibers to the impregnation die, uniformly impregnating the polyolefin resin melted between the filaments, and then cutting to the required length. Can get to.
  • the impregnation die provided at the tip of the extruder, the molten resin is supplied from the extruder, while the continuous glass fiber bundle is allowed to pass through, and the glass fiber bundle is impregnated with the molten resin, and then drawn through a nozzle.
  • a method of pelletizing to the required length is taken.
  • a polyolefin resin, an unsaturated carboxylic acid or an anhydride thereof, an organic peroxide, or the like may be dry blended, introduced into a hopper of an extruder, and supplied while being simultaneously modified.
  • the method for impregnation is not particularly limited, and a method in which roving is passed through a resin powder fluidized bed and then heated above the melting point of the resin (Japanese Patent Laid-Open No. Sho 46-4545), using a crosshead die A method of impregnating a roving of reinforcing fibers with a molten thermoplastic resin (Japanese Patent Laid-Open Nos. 62-60625, 63-1332036, 63-264326, and 1-208118) ), A method in which resin fibers and rovings of reinforcing fibers are mixed and then heated above the melting point of the resin to impregnate the resin (Japanese Patent Laid-Open No.
  • an extruder with two or more feed parts, separate from the top feed, the resin and resin decomposer (in the case of polypropylene resin, organic peroxide is preferable), and side feed.
  • the resin may be added.
  • Two or more extruders may be used, and one or more of the extruders may be charged with a resin and a resin decomposing agent (in the case of polypropylene resin, an organic peroxide is preferable).
  • a resin, an unsaturated carboxylic acid and a derivative thereof, and a decomposition agent in the case of polypropylene resin, an organic peroxide is preferable
  • a decomposition agent in the case of polypropylene resin, an organic peroxide is preferable
  • the long fiber reinforced resin composition of the present invention contains a polyolefin resin (component (B)) satisfying the following (B-1) and (B-2).
  • B-1) Polyolefin resin melt index (resin temperature: 230 ° C., load: 21.18 N) is 20 to 70 g / 10 min.
  • the polyolefin resin as the component (B) is not particularly limited as long as the above (B-1) and (B-2) are satisfied, but a polyethylene resin (for example, low density polyethylene (LDPE), ethylene- ⁇ -olefin copolymer) is not limited. Polymer), polypropylene resin, and the like. Preferably, it is a polypropylene resin.
  • Polypropylene resins include propylene homopolymers, propylene- ⁇ -olefin random copolymers, propylene- ⁇ -olefin block copolymers, and the like.
  • the melt index (resin temperature: 230 ° C., load: 21.18 N) of the polyolefin-based resin is 20 to 70 g / 10 minutes, preferably 20 to 60 g / 10 minutes.
  • the melt index of the polyolefin-based resin is less than 20 g / 10 minutes, the fluidity of the resin composition is lowered and the mold transfer may be lowered.
  • the melt index of the polyolefin-based resin is more than 70 g / 10 minutes, there is a possibility that the unopened glass fiber increases.
  • the method for adjusting the melt index of the polyolefin resin to the above range is as described in the component (A).
  • G ′′ ⁇ ⁇ that is, G ′ ⁇ G ′′ is 0.23 (sec) or less (relaxation time ⁇ ⁇ 0.23 (sec)).
  • the relaxation time of the polyolefin-based resin is usually 0.01 to 0.23 (sec), preferably 0.05 to 0.2 (sec).
  • the definition and adjustment method of the relaxation time ⁇ are as described in the component (A).
  • the long fiber reinforced resin composition of the present invention comprises the component (A) and the component (B) described above, the content of the component (A) is 50 to 90 wt%, and the content of the component (B) is 10 to 50 wt%.
  • the composition ratio of component (A) to component (B) is preferably such that the content of component (A) is 50 to 80 wt% and the content of component (B) is 20 to 50 wt%.
  • the content of the reinforcing fiber contained in the long fiber reinforced resin composition of the present invention is 20 to 60 wt%, preferably 25 to 40 wt% with respect to the total length of the long fiber reinforced resin composition. If the reinforcing fiber content is less than 20 wt%, the strength of the resulting molded product may be insufficient, and if the reinforcing fiber content exceeds 60 wt%, the appearance may be poor.
  • the long fiber reinforced resin composition of the present invention may consist essentially of the above component (A) and component (B), or may consist solely of these components. “Substantially” means that the composition is composed of only component (A) and component (B), and may contain the following additives in addition to these components.
  • composition of the present invention has various other additives depending on applications, such as dispersants, lubricants, plasticizers, flame retardants, antioxidants (phenolic antioxidants, phosphoric antioxidants, sulfur-based oxidations). Inhibitors), antistatic agents, light stabilizers, ultraviolet absorbers, crystallization accelerators (nucleating agents), foaming agents, crosslinking agents, modifying additives such as antibacterial agents, colorants such as pigments and dyes, Carbon black, titanium oxide, bengara, azo pigment, anthraquinone pigment, phthalocyanine, talc, calcium carbonate, mica, clay and other particulate fillers, short fiber fillers such as wollastonite, whisker such as potassium titanate Can be added. These additives may be added during pellet production and contained in the pellet, or may be added during production of the molded body.
  • the manufacturing method in particular of the long fiber reinforced resin composition of this invention is not restrict
  • the production conditions are not particularly limited, and can be appropriately adjusted according to the type of material used.
  • component (A) and component (B) are blended in a dry blend, in order to maintain the fiber length in the composition and obtain higher rigidity, impact resistance, and durability improvement effects, It is preferable to directly use a molding machine such as an injection molding machine without passing through an extruder.
  • the long fiber reinforced resin composition of the present invention can be molded to produce various molded bodies.
  • a known molding method such as an injection molding method, an extrusion molding method, a hollow molding method, a compression molding method, an injection compression molding method, a gas injection injection molding or a foam injection molding can be applied without any limitation.
  • an injection molding method, a compression molding method, and an injection compression molding method are preferable.
  • the molded body obtained from the long fiber reinforced resin composition of the present invention is excellent in appearance because the reinforcing fibers are sufficiently opened. Further, since the length of the reinforcing fiber is kept long, the physical properties equivalent to or higher than those of the conventional product can be maintained.
  • MI Melt index
  • Example 1 Long fiber reinforced thermoplastic resin pellets were manufactured using the pellet manufacturing apparatus shown in FIG.
  • 10 is a die
  • 20 is an extruder that supplies thermoplastic molten resin to the die
  • 30 is a roll of a fiber bundle F
  • 40 is a tension that gives a certain tension to the fiber bundle F drawn into the die 10.
  • a roll group, 50 is a cooling means for cooling the molten resin-impregnated fiber bundle drawn from the die 10
  • 60 is a fiber bundle drawing roll
  • 70 is a long-fiber reinforced heat by cutting the drawn molten resin-impregnated fiber bundle.
  • It is a pelletizer to make a plastic resin pellet.
  • three independent fiber bundles F are simultaneously impregnated with molten resin.
  • the PP-A is a propylene homopolymer (Y-6005GM, manufactured by Prime Polymer Co., Ltd.) and a peroxide bis (tert-butyldioxyisopropyl) benzene (Perkadox 14, manufactured by Kayaku Akzo Co., Ltd.). Is 0.1% by weight of propylene homopolymer obtained by melt kneading.
  • the tension roll group was fed into the die while adjusting the amount of the fiber bundle, impregnated, then cooled by pulling out from the die, and a pellet length 6 mm long fiber reinforced thermoplastic resin pellet was prepared with a pelletizer. .
  • PP-F was blended with the obtained pellets at a blending ratio shown in Table 2 so that the glass fiber content of the resulting composition was 40 wt%, to prepare a long fiber reinforced resin composition.
  • PP-F is a propylene homopolymer obtained by mixing 30 parts by weight of propylene homopolymer Y-6005GM and 70 parts by weight of propylene homopolymer Y-900GV (manufactured by Prime Polymer Co., Ltd.).
  • the prepared composition was introduced into an injection molding machine (AZ7000, manufactured by Nissei Plastic Industry Co., Ltd.), and 10 plate-shaped molded bodies of 200 mm ⁇ 180 mm ⁇ 3 mm were produced.
  • AZ7000 manufactured by Nissei Plastic Industry Co., Ltd.
  • a film gate was used as a mold and a full flight screw was used as a screw. Molding was performed under the conditions of a resin temperature of 250 ° C., a mold temperature of 45 ° C., and a filling speed of 20 mm / sec.
  • unopened index (number of unopened fibers of B) ⁇ (number of unopened fibers of A) ⁇ 100.
  • Examples 2 and 3 and Comparative Examples 1 to 6 A long fiber thermoplastic resin pellet and a composition were prepared in the same composition ratio as shown in Table 2 using the thermoplastic resin, the modified polyolefin resin and the polyolefin resin shown in Table 1, and were the same as in Example 1. Fiber thermoplastic resin pellets, compositions and molded bodies were prepared and evaluated. The results are shown in Table 2.
  • Molded articles formed by molding the long fiber reinforced resin composition of the present invention include automotive parts (front end, fan sheroud, cooling fan, engine under cover, engine cover, radiator box, side door, back door inner, back door outer. , Outer panels, fenders, roof rails, door handles, luggage boxes, wheel covers, handles), motorcycle and bicycle parts (luggage boxes, handles, wheels), housing-related parts (hot water cleaning valve seat parts, bathroom parts, bathtub parts, chairs) Legs, valves, meter boxes), washing machine parts (bathtubs, balance rings, etc.), fans for wind power generators, power tool parts, mower handles, hose joints, and the like.
  • automotive parts front end, fan sheroud, cooling fan, engine under cover, engine cover, radiator box, side door, back door inner, back door outer.

Abstract

L'invention porte sur une composition de résine renforcée par des fibres longues comprenant 50 à 90 % en poids d'un composant (A) et 10 à 50 % en poids d'un composant (B), le composant (A) contenant des fibres de renforcement à une teneur de 20 à 60 % en poids par rapport à la quantité totale de la composition de résine renforcée par des fibres longues. [Composant (A)] Une pastille de résine thermoplastique renforcée par des fibres longues qui comprend une résine thermoplastique, une résine de polyoléfine modifiée qui a été modifiée par un acide carboxylique insaturé ou un dérivé de celui-ci et des fibres de renforcement, et qui satisfait aux exigences suivantes (A-1) et (A-2) : (A-1) la résine thermoplastique a un indice de fluage à chaud de 100 à 250 g/10 min; et (A-2) la résine thermoplastique a un temps de relaxation (λ) de 0,1 (s) ou moins. [Composant (B)] Une résine de polyoléfine qui satisfait aux exigences suivantes (B-1) et (B-2) : (B-1) la résine de polyoléfine a un indice de fluage à chaud de 20 à 70 g/10 min; et (B-2) la résine de polyoléfine a un temps de relaxation (λ) de 0,23 (s) ou moins.
PCT/JP2009/055388 2008-03-21 2009-03-19 Composition de résine renforcée par des fibres longues et article moulé à base de cette composition WO2009116608A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
JP2010503917A JPWO2009116608A1 (ja) 2008-03-21 2009-03-19 長繊維強化樹脂組成物及びその成形体
CN200980109941.6A CN102159627B (zh) 2008-03-21 2009-03-19 长纤维增强树脂组合物及其成型体
US12/922,348 US9359492B2 (en) 2008-03-21 2009-03-19 Long-fiber-reinforced resin composition and molded article thereof
EP09722098.2A EP2256150B1 (fr) 2008-03-21 2009-03-19 Composition de résine renforcée par des fibres longues et article moulé à base de cette composition
BRPI0908954A BRPI0908954A2 (pt) 2008-03-21 2009-03-19 composição de resina reforçada por fibra longa moldado da mesma
US15/139,547 US20160237269A1 (en) 2008-03-21 2016-04-27 Long-fiber-reinforced resin composition and molded article thereof

Applications Claiming Priority (2)

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JP2008-074405 2008-03-21
JP2008074405 2008-03-21

Related Child Applications (2)

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US12/922,348 A-371-Of-International US9359492B2 (en) 2008-03-21 2009-03-19 Long-fiber-reinforced resin composition and molded article thereof
US15/139,547 Continuation US20160237269A1 (en) 2008-03-21 2016-04-27 Long-fiber-reinforced resin composition and molded article thereof

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EP2345689A1 (fr) * 2008-09-30 2011-07-20 Mitsui Chemicals, Inc. Composition de résine renforcée par des fibres et objet moulé fabriqué à partir de celle-ci
KR20200010481A (ko) * 2017-07-28 2020-01-30 보레알리스 아게 긴 탄소 섬유 강화 폴리프로필렌 조성물
WO2020091051A1 (fr) * 2018-11-02 2020-05-07 株式会社プライムポリマー Composition de résine à base de propylène renforcée de fibres longues et corps moulé renforcé de fibres longues
WO2021029275A1 (fr) * 2019-08-09 2021-02-18 住友化学株式会社 Pastille de résine de polyester à cristaux liquides, son procédé de production, et procédé de production d'un article moulé
JP2021028374A (ja) * 2019-08-09 2021-02-25 住友化学株式会社 樹脂組成物及び成形体

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US20110263738A1 (en) * 2008-12-24 2011-10-27 Kuraray Co., Ltd. Expansion molded body and method for producing expansion molded body
JP6099038B2 (ja) * 2012-11-13 2017-03-22 日本ケミコン株式会社 電極材料の製造方法
CN116141570A (zh) 2015-09-04 2023-05-23 沙特基础工业全球技术公司 通过在塑化期间溶解气体在注塑成型的固体零件中生产较长纤维的方法
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EP2345689A1 (fr) * 2008-09-30 2011-07-20 Mitsui Chemicals, Inc. Composition de résine renforcée par des fibres et objet moulé fabriqué à partir de celle-ci
EP2345689A4 (fr) * 2008-09-30 2012-08-29 Mitsui Chemicals Inc Composition de résine renforcée par des fibres et objet moulé fabriqué à partir de celle-ci
US8420728B2 (en) 2008-09-30 2013-04-16 Mitsui Chemicals, Inc. Fiber-reinforced resin composition and molded body thereof
WO2010137305A1 (fr) * 2009-05-29 2010-12-02 株式会社プライムポリマー Composition de résine renforcée de fibres longues et objet moulé fait de celle-ci
KR20200010481A (ko) * 2017-07-28 2020-01-30 보레알리스 아게 긴 탄소 섬유 강화 폴리프로필렌 조성물
KR102270881B1 (ko) 2017-07-28 2021-06-30 보레알리스 아게 긴 탄소 섬유 강화 폴리프로필렌 조성물
WO2020091051A1 (fr) * 2018-11-02 2020-05-07 株式会社プライムポリマー Composition de résine à base de propylène renforcée de fibres longues et corps moulé renforcé de fibres longues
JPWO2020091051A1 (ja) * 2018-11-02 2021-09-24 株式会社プライムポリマー 長繊維強化プロピレン系樹脂組成物および長繊維強化成形体
JP7198287B2 (ja) 2018-11-02 2022-12-28 株式会社プライムポリマー 長繊維強化プロピレン系樹脂組成物および長繊維強化成形体
WO2021029275A1 (fr) * 2019-08-09 2021-02-18 住友化学株式会社 Pastille de résine de polyester à cristaux liquides, son procédé de production, et procédé de production d'un article moulé
JP2021028374A (ja) * 2019-08-09 2021-02-25 住友化学株式会社 樹脂組成物及び成形体
JP2021028373A (ja) * 2019-08-09 2021-02-25 住友化学株式会社 液晶ポリエステル樹脂ペレット、及びその製造方法、並びに成形体の製造方法

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EP2256150A4 (fr) 2011-12-14
US20160237269A1 (en) 2016-08-18
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EP2256150B1 (fr) 2013-05-22
JPWO2009116608A1 (ja) 2011-07-21
CN102159627A (zh) 2011-08-17
US20110040022A1 (en) 2011-02-17
US9359492B2 (en) 2016-06-07
BRPI0908954A2 (pt) 2020-05-19

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